Split type NMR Superconductive magnet device and NMR apparatus for solution analysis with a permanent current switch holding the split type superconducting magnet in a permanent current mode

ABSTRACT

A superconducting magnet device configured for an NMR spectrometer includes a split type superconducting magnet having left and right solenoid superconducting magnets, wherein the split type superconducting magnet has a center space around a vertical center axis between the left and right solenoid superconducting magnets, a sample tube placed in the center space in order to enable placement of a sample therein, which is energized by the magnetic field generated by the split type superconducting magnet, a solenoid coil configured for detecting signals due to magnetic resonance from the energized sample, and a permanent current switch for holding the split type superconducting magnet to a permanent current mode.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of U.S. application Ser. No. 11/078,360 filedMar. 14, 2005, which is a continuation of U.S. application Ser. No.10/430,340, filed May 7, 2003 now ABANDONED, the contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a nuclear magnetic resonance analyzingapparatus; and, more particularly, the invention relates to a magnetdevice for generating a uniform magnetic field.

Rapid progress has recently been made in the field of organic analysisusing nuclear magnetic resonance. In particular, atomic structures oforganic compounds, such as proteins, can now be efficiently analyzed bythe combined use of nuclear magnetic resonance and superconductingferromagnetic technology.

An object of the present invention is to provide an NMR spectrometerwhich is necessary for analyzing atomic structures and interactions ofprotein molecules in a solution (the solution is prepared by dissolvingminute amounts of proteins into a liquid). The NMR spectrometer of thepresent invention is a special energy spectrometer, which is differentfrom a medical MRI diagnosing apparatus having an image resolution inthe order of a millimeter, of the type used for human tomography. Such aspecial energy spectrometer must have a magnetic field intensity whichis higher than that of the typical medical MRI diagnosing apparatus byone digit, a magnetic field uniformity which is higher than that of themedical MRI diagnosing apparatus by four digits, and a stability whichis higher than that of the typical medical typical MRI diagnosingapparatus by three digits; and, the design engineering and manufacturingtechnology thereof are totally different from those of the typicalmedical MRI diagnosing apparatus.

Details of the conventional high-resolution nuclear magnetic resonanceanalyzing apparatuses can be found in “NMR of Proteins”, which waswritten by Yohji Arata and published by Kyoritsu Shuppan in 1996. Recentpublications relating to typical equipment components to be utilized forapplying NMR to protein analysis include: Japanese Patent Laid-open No.2000-147082, which discloses a development relating to a superconductingmagnet, i.e., multilayer air-core solenoid coils; U.S. Pat. No.6,121,776, which discloses a birdcage superconducting detection coil;Japanese Patent laid-open Nos. 2000-266830 and 6-237912, each of whichdiscloses a signal detection technique using a conventional saddle-likecoil or a birdcage coil; and so forth.

According to the above-listed publications, all of the conventional highsensitivity nuclear magnetic resonance analyzing apparatuses for proteinanalysis include a superconducting magnet device which uses solenoidcoils that are combined so as to generate a magnetic field in a verticaldirection, thereby irradiating a sample with an electromagnetic wave of400 to 900 MHz so as to detect a resonance waveform produced from thesample by the use of a saddle-like or birdcage detection coil. In somecases, the S/N parameter is improved by the use of a detector which iscooled to a low temperature in order to reduce the thermal noise in thedetection of signals, as disclosed in the above-mentioned United StatesPatent.

In the past, the sensitivity of high sensitivity nuclear magneticresonance apparatuses has been improved through the use of methods ofimproving the intensity at the center portion of the magnetic field ofthe superconducting magnet, without changing the basic system structureof the apparatus, including an antenna, a magnet, and so forth.Therefore, although the maximum NMR detection sensitivity, which hasheretofore been reported, was achieved by an NMR apparatus of 900 MHz,which uses a large superconducting magnet, such as shown in of FIG. 8,having a center magnetic field intensity of 21.1 Tesla, the basicstructure of the NMR apparatus is not any different from that disclosedin Japanese Patent Laid-open No. 2000-147082. For better understandingof the basic structure, a sectional perspective view of thesuperconducting coils of the NMR apparatus is shown in FIG. 9, wherein avirtual central axis is indicated. In protein analysis using a solution,an increase in the intensity at the magnetic field center has theeffects of improving the sensitivity and clarifying the separation of achemical shift.

The sensitivity improving effects, which depend on the shapes of thedetection coils, are mentioned on page 326 of “Book of NMR”, which waswritten by Yohji Arata and published by Maruzen in 2000, where thesolenoid coil is indicated as being advantageous as compared with thesaddle-like coil or the birdcage coil in various aspects, as describedbelow.

For example, the solenoid coil is superior in controllability ofimpedance, filling factor, and RF magnetic field efficiency. Accordingto the “Book of NMR”, however, it is actually impossible to windsolenoid coils around a sample tube which is placed perpendicularly withrespect to the magnetic field in the conventional superconducting magnetstructure; and, in general, the solenoid coil has not been used in caseswhere the sensitivity is crucial, such as a case of determining a minuteamount of protein dissolved in a solution. For a particularlyexceptional case wherein the solenoid coil is used for determining aminute amount of sample solution with high sensitivity, a method whichemploys a specially designed micro sample tube and a probe combined withthe solenoid coil is known.

As a particular example, a method wherein a high-temperaturesuperconducting bulk magnet is magnetized in the horizontal direction,so as to detect NMR signals using a solenoid coil, is disclosed inJapanese Patent Laid-open No. 11-248810. Japanese Patent Laid-open No.7-240310 discloses the structures of a superconducting magnet and acooling container that are suitably used for a typical NMR apparatus foreliminating a restriction in the height of the apparatus. However, amethod of achieving the detection sensitivity which is required foranalyzing proteins, and techniques for controlling the uniformity andthe time stability of a magnetic field, have not yet been proposed.

SUMMARY OF THE INVENTION

Recently, the need for analysis of samples which contain proteins, eachhaving a low solubility in water, has grown with the increase in theneed for investigations of proteins, and such a growing need has broughtabout the necessity of improving the sensitivity for detecting NMR. Inorder to adapt a nuclear magnetic resonance analyzing apparatus for theneeds described above, it is necessary to improve the detectionsensitivity, without increasing the size of the sample space as comparedwith conventional apparatuses and, further, it is mandatory to providestability in a superconducting magnetic field for a long period of dataintegration. The improved sensitivity contributes not only to thereduction in detection time, but also to the reduction in sample amount,thereby achieving the effect of enabling the analysis of proteins havinga low solubility to liquids. Thus, it is required that the NMR analyzingapparatus, which is to be used for the protein analysis, have aparticularly superior detection sensitivity and stability as comparedwith the conventional ones, and accurate and stable NMR signal detectionover a long period of time, such as a week or more, must be assured.This is because a fluctuation in the magnetic field during the detectioncauses a peak of the NMR signals to move, and such movement of the peakin detection of an interaction can be confused with movement of a peakcaused by the interaction or by an unstable magnetic field. Further, ifthe magnetic field is non-uniform, desired peaks are overlapped to causeproblems, such as difficulty in distinguishing the interaction. Thus,the future NMR technology to be used for the purpose of analyzingproteins must be a novel technology, which involves more than a simplemodification of the conventional NMR apparatuses.

For example, the specifications for a uniformity of a magnetic fieldprovided in a typical NMR apparatus are 0.01 ppm in a sample space and0.01 ppm/h by time stability. If this magnetic field is used in atypical proton NMR apparatus of 600 MHz, the allowable error is 6 Hz.However, for the analysis of interactions of proteins, the requiredspace and time resolutions are not more than 1.0 Hz, preferably not morethan 0.5 Hz.

The superconducting magnet and the detection coil must be optimized soas to achieve the above-identified uniformity and time stability in themagnetic field. Therefore, the performances of the conventional NMRapparatuses are insufficient, and the required stability and uniformityare greater than those achieved by the conventional NMR apparatuses byone digit or more.

Since the improvements in sensitivity of the conventional NMRapparatuses have been achieved by intensifying the magnetic field, theapparatuses have become too large. Since a dedicated room was requiredfor the apparatuses in view of the leakage magnetic field and the floorstrength, problems such as poor installability have arisen. Also, anincrease in the cost of the superconducting magnet has been problematic.Further, in the improvement in sensitivity achieved by the conventionaltechnique, the intensity has reached to its upper limit of 21 T due tothe restriction caused by the critical magnetic field of thesuperconducting material. Therefore, in order to achieve a furtherimprovement in sensitivity, there has been a demand for a new techniquefor improving the detection sensitivity which does not rely on themagnetic field intensity.

High-sensitivity detection using a solenoid coil can be realized by theuse of a special sample tube which contains a minute amount of a sampleand a special detection probe, as mentioned above; however, thehigh-sensitivity detection method is not suitable for analyzing aprotein solution that is as little as about 10 cc. Further, according tothe technique, wherein a magnetic field is generated in the horizontaldirection by the use of a ferromagnetic member and NMR signals aredetected by the use of the solenoid coil, which is disclosed in JapanesePatent Laid-open No. 11-248810, a magnetic field that is less than 10 Tis generated on the surface of the high temperature superconductor,while the magnetic field near the sample has an intensity of severalteslas at most. Therefore, it is impossible to achieve a magnetic fieldof 11 T or more, preferably 14.1 T or more, which is required forprotein analysis in a desired sample space, through the use of thetechnology disclosed in Japanese Patent Laid-open No. 11-248810.

Further, the technique disclosed in Japanese Patent Laid-open No.11-248810 involves a difficulty in achieving a time stability of 1.0Hz/time or less, which is required for protein analysis, due to themagnetic flux creep of the superconductors. Further, this technique alsoinvolves a difficulty in achieving a magnetic field uniformity of 1.0 Hzor less in the proton nuclear magnetic resonance frequency, which isrequired for protein analysis, in a space having a diameter of 10 mm anda length of 20 mm, since there is a non-uniformity derived from theprocess of manufacture of the material of the superconducting bulkmagnet.

Thus, break-through developments in the technology to fit therequirements for protein analysis are in demand, while an improvement inthe sensitivity achieved by increasing the magnetic field intensity hasreached its limit. Therefore, a novel technique for further improvementthe in sensitivity has been in demand.

To provide efficient, accurate analysis of the interactions of proteinswith low molecular weight molecules, such as a substrate and ligand in asolution, for which the need will hereafter increase, it is desirablethat the analysis be conducted by using an appropriate amount of samplewith a frequency of 600 to 900 MHz and an intensity at the magneticfield center of about 14 to 21 T, and that the detection sensitivity andthroughput be increased.

In general, in an apparatus of 800 MHz or more, liquid helium of 4.2 Kis depressurized and supercooled to 1.8 K in order to exploit thesuperconductivity to the utmost. Therefore, the operation of theapparatus is complicated and very careful maintenance therefor isnecessary.

Further, since the leakage magnetic field is increased with an increasein the size of the magnetic device, a dedicated room is usually requiredfor the conventional NMR apparatus. In particular, from the standpointof the installability of the apparatus, the conventional magnetic devicehas a problem of a leakage magnetic field which is increased in thevertical direction with an increase in the intensity at the magneticfield center. For example, since the conventional class 900 MHz magnetdevice generates a leakage magnetic field as long as 5 m in height, aroom having a considerable ceiling height is required.

Thus, the conventional magnet device has the problem of increased costfor installation. In addition, the magnet portion of the conventional900 MHz superconducting magnet has a diameter of 1.86 m and a height ofa several meters, as is disclosed in “IEEE. Transactions on AppliedSuperconductivity, Vol. 11, No. 1, p. 2438”.

An object of the present invention is to provide a novel nuclearmagnetic resonance analyzing apparatus in which the detectionsensitivity of NMR signals is improved by 40% or more at a frequency of600 MHz (14.1 T) with respect to the conventional apparatuses in a statewhere an ordinary sample tube having a diameter of 5 to 10 mm andcontaining a sample solution of 30 mm is placed therein, and in which atime stability and a space uniformity of the superconducting magnetrequired for protein analysis are provided. The present invention not beassumed to limit the operation temperature to 4.2 K in structure. It ispossible to realize the ultimate performance through the application ofthe present invention; and, depending on the mode of the application,the apparatus of the present invention may be operated with theconventional upper limit magnetic field intensity of 21.1 T, i.e., 900MHz and 1.8 K. In this case, the apparatus of the present invention isable to exhibit an improved sensitivity by 40% as compared with theconventional apparatuses, thereby advancing the upper limit of thedetection sensitivity for the first time in the art.

The inventors of the present invention have conducted intensive studiesto discover problems in the conventional nuclear magnetic resonanceapparatuses and solutions thereto. Since the existing nuclear magneticresonance apparatuses have been developed from the standpoint of bothcost and installability, NMR signals produced from a solution sampleplaced at the center portion of multilayer air-core solenoid coilshaving an excellent magnetic field uniformity have been detected by theuse of a saddle-like or birdcage antenna. In the past, with thedevelopment in NMR technology attained by the progress achieved in thedetection technique and the analysis method, the detection sensitivityhas been improved through the enhancement of the intensity at themagnetic field center from a magnetic field intensity of less than 400MHz without changing the basic structure. Further, use of thesuperconducting birdcage antenna for the reduction of thermal noise hasrecently been proposed. The inventors have conducted intensive studieson a technique for remarkably enhancing the signal intensity withoutchanging the magnetic field intensity. As a result, we have found thatthe novel structure described below can solve the problems describedabove.

The present invention enables an improvement in the sensitivity by usinga solenoid detection coil having a diameter of about 5 to 10 mm and aheight of about 20 mm, with which an ordinary sample tube for NMRinvestigations can be used, in a sample space having a diameter of 5 to10 mm and in a magnetic field of not less than 400 MHz, preferably about600 to 900 MHz, which is suitable for a solution NMR of a height of 20mm.

In theory, it is expected that the sensitively of 1.4 (√{square rootover ( )}2) times that achieved by the conventional devices is achievedby the shape of the coil, and further improvement is expected by otherfactors. Also, the data integration time can be shortened to not morethan half that of the conventional devices. A sample tube having adiameter of 5 to 10 mm is charged with a liquid sample until it reachesa height of 20 to 30 mm, and then it is inserted into the apparatus fromabove along the vertical direction. In order to detect the NMR signalswith high sensitivity by use of the solenoid coil which is wound about avertical axis, it is necessary to magnetize a magnetic field to begenerated by the superconducting magnet in the horizontal direction andto make it possible to place the solution sample, which can readily beattached and removed, at the center portion of the magnetic field.

Therefore, the structure of the superconducting magnet device of thepresent invention is different from that of the conventional deviceswhich use a simple solenoid magnet, and, thereby, it is necessary thatthe superconducting magnet be a split type magnet having a pair of leftand right magnet portions. It is necessary that the magnet to be usedfor the NMR apparatus generate a magnetic field of ppb-order uniformityin the sample space, as mentioned above. A technique for achieving suchuniformity of the magnetic field using the high magnetic field splittype magnet of 14.1 T has not been proposed in the art. As shown in FIG.10, the present invention is characterized in that a current conveyed bycoils constituting the innermost layer, among two sets of multilayercoils facing each other with a predetermined spacing, flows in adirection reverse from that of the main magnetic field.

Referring to FIG. 10, the arrow indicated in FIG. 10 is a virtualcentral axis of coils 1 to 5 and 1′ to 5′ constituting the magnet. Sinceeach of the coils is wound around a spool, which is not shown in FIG.10, a section thereof typically has a substantially rectangular shape,as shown in FIG. 10. Also, in order to facilitate fabrication of themagnet, it is desirable to reduce the number of spools. Therefore, asthe coils 4 and 5 of FIG. 10, coils having a substantially identicalinner diameter are usually wound around an identical spool. Inaccordance with the present invention, the coils, such as the coils 4and 5, which have a substantially identical inner diameter, asubstantially identical central radius or a substantially identicalouter diameter, as seen in their sectional views, are referred to ascoils forming an identical layer.

In order to generate a uniform magnetic field at a central part of themagnet where a sample is inserted, it is necessary to use coils, whichgenerate a magnetic field in a direction reverse from that of the mainmagnetic field, as the coils for constituting the innermost layer in thesplit type magnet of the present invention. The reasons for such arequirement will be explained hereinafter.

FIG. 12 is a sectional view showing a two-dimensional axisymmetricaldistribution of currents. As is well-known, a uniform magnetic field isgenerated in an inner space of the current distribution by setting acurrent I(θ) of an angle θ, when the center axis is the z axis, to be aso-called cosine θ distribution, as represented by the followingexpression.I(θ)=A cos(θ)In the above expression, A is a proportional constant. Generation of auniform magnetic field by the use of a limited number of coils meansdiscretization of the current distribution shown in FIG. 12. However, ascan be understood qualitatively, it is difficult to discretize thecurrents in a region between the two dotted lines of FIG. 12 outside theregion through the discretization of the unidirectional currentdistribution of FIG. 12 using split type coils. It is possible toovercome this difficulty by using expressions for the magnetic fieldgenerated by an annulus current, as follows referring to FIG. 13, an Xaxis and a Y axis show a plane on which Z=0. It is possible to representthe z component of a magnetic field having axes X, Y and Z, which isgenerated at the point P (r, 0), where r and θ are sphericalcoordinates, in an inner region of a sphere formed by the inscribing ofthe annulus current I to the annulus ring, as shown in FIG. 13, by thefollowing expressions.

$B_{z} = {\sum\limits_{n = 0}{A_{n}r^{n}{P_{n}\left( {\cos\;\theta} \right)}}}$

$A_{n} = {\frac{\mu_{0}I}{2\; f^{n + 1}}\sin\;\alpha\;{P_{n + 1}^{1}\left( {\cos\;\alpha} \right)}}$In the above expressions, A_(n) represents the intensity of the n-thorder magnetic field. As shown in FIG. 13, for example θ and α representangles and r and f represent distances Since the magnet of the presentinvention is mirror-symmetrical with respect to the center plane, onlythe even-order magnetic fields should be considered due to the symmetry.It is possible to generate a uniform magnetic field by setting a sum ofthe second-order irregular magnetic fields to zero. FIGS. 14 to 16 showgraphs, in each of which the magnetic field intensity (A₂, A₄, and A₆,respectively) is plotted with respect to α (degrees). In the graphs, itis indicated that μ₀I/2/f^(n+1)=1. As shown in FIGS. 15 and 16, sinceeach of the higher-order magnetic fields takes positive and negativevalues with respect to α, the sum of the magnetic fields of all thecoils can readily be set to zero, if the arrangement and magnetomotiveforces of the discrete coils are properly set. In turn, the second-ordermagnetic field shown in FIG. 14 becomes zero when tan α=2. This positionis well-known as a Helmholtz coil. As is apparent from FIG. 14, when αis smaller than the α of tan α=2 (about 63.4 degrees), the secondmagnetic field takes only a positive value. As is apparent from FIGS. 1,2, and 10, since almost all of the coils are placed at positions where αis smaller than the above-described α (about 63.4 degrees), in the splittype coil arrangement, it is impossible to set the total of second-orderirregular magnetic fields generated by the coils having a current in thedirection (positive direction) identical with that generating the mainmagnetic field to zero. Therefore, it is necessary to use coils having acurrent in a direction reverse (negative direction) to that generatingthe main magnetic field, and it is desirable that a portion at which thecoils are to be arranged be such that the radius of each of the coils issmaller than those of other coils. The reasons for the desiredarrangement will be explained hereinafter. The intensity of an irregularmagnetic field generated by the annulus current I, which is shown inFIG. 13, is inversely proportional to f^(n+1) according to theabove-identified expressions. Therefore, a smaller radius of the annuluscurrent is more advantageous for generating A₀, i.e., a negativesecond-order irregular magnetic field, without impairing the intensityof the main magnetic field. In principle, it is possible to set thesecond-order irregular magnetic field to zero by the use of negativecurrent coils having a large radius; however, in view of the abovereasons, such negative current coils are unrealistic as means forforming the high magnetic field generating magnet, which is the subjectof the present invention, since they reduce the intensity of the mainmagnetic field. In view of the above reasons, negative-direction currentcoils are necessarily used for the coils which form the innermost layer,i.e., the coils having an inner diameter, a central radius or an outerdiameter, as seen in their sectional views.

BRIEF DESCRIPTION OF THE DRAWINGS

Other objects and advantages of the present invention will becomeapparent from the following description of various embodiments withreference to the accompanying drawings, in which:

FIG. 1 is a sectional view schematically showing an NMR apparatusaccording to a first embodiment of the present invention;

FIG. 2 is a sectional view schematically showing an arrangement of coilsof a split type magnet device according to a second embodiment of thepresent invention;

FIG. 3 is a sectional view schematically showing an arrangement of coilsof a split type magnet device according to a third embodiment of thepresent invention;

FIG. 4 is a sectional view schematically showing an arrangement of coilsof a split type magnet device according to a fourth embodiment of thepresent invention;

FIG. 5 is a sectional view schematically showing an arrangement of coilsof a split type magnet device and a ferromagnetic member for shieldingleakage magnetic field according to a fifth embodiment of the presentinvention;

FIG. 6 is a sectional view schematically showing an arrangement of coilsof a split type magnet device and a ferromagnetic member for shieldingleakage magnetic field according to a sixth embodiment of the presentinvention;

FIG. 7 is a sectional view schematically showing an arrangement of coilsof a split type magnet device and a ferromagnetic member for shieldingleakage magnetic field according to a seventh embodiment of the presentinvention;

FIG. 8 is a sectional view schematically showing a conventional NMRapparatus;

FIG. 9 is a sectional perspective view showing superconducting coilsconstituting the conventional NMR apparatus;

FIG. 10 is a sectional perspective view showing coils of a split typemagnet device according to an embodiment of the present invention;

FIG. 11 is a diagram showing the NMR apparatus of the present invention;

FIG. 12 is a diagram, for the purpose of illustrating an effect of thepresent invention, showing a two-dimensional axisymmetrical distributionof currents;

FIG. 13 is a diagram, for the purpose of illustrating an effect of thepresent invention, showing a positional relationship between the currentI which is represented by the position (f,α) and r,θ;

FIG. 14 is a graph showing, for the purpose of illustrating an effect ofthe present invention, a relationship between a second-order irregularmagnetic field generated by the current I, which is represented by theposition (f,α) and the angle α;

FIG. 15 is a graph showing, for the purpose of illustrating an effect ofthe present invention, a relationship between a fourth-order irregularmagnetic field generated by the current I, which is represented by theposition (f,α) and the angle α; and

FIG. 16 is a graph showing, for the purpose of illustrating an effect ofthe present invention, a relationship between a sixth-order irregularmagnetic field generated by the current I, which is represented by theposition (f,α) and the angle α.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Specific embodiments of the present invention will be describedhereinafter. FIG. 11 is a diagram showing an NMR apparatus using a splittype magnet. A superconducting magnet 39, which is formed of splitcoils, is installed with a virtual central axis thereof extending alonga substantially horizontal direction. A protein sample 40 is insertedinto the apparatus from above, and a uniform static magnetic field isapplied, from the horizontal direction, to the protein sample 40. Sincea solenoid coil 41 is used for receiving an NMR signal, SN ratio isimproved by 40% as compared with that achieved by the conventionalmethod, wherein a saddle-like or a birdcage solenoid coil is used, asmentioned in the foregoing. The superconducting magnet 39 is maintainedat a permanent current mode by using a permanent current switch 42. Thecoils constituting the superconducting magnet 39 are connected with oneanother, with the superconductive state being maintained by asuperconducting connection 43. The superconducting magnet 39 is cooledand kept at a low temperature by liquid helium stored in a liquid heliumtank 44. The helium tank 44 is surrounded by a liquid nitrogen tank 45to establish a dual structure made up of the helium tank 44 and thenitrogen tank 45, so that evaporation of the liquid helium issuppressed. The NMR apparatus as a whole is supported by vibration proofsupports 46.

FIG. 1 is a sectional view showing the superconducting magnet of the NMRapparatus according to the present invention, and FIG. 10 is a sectionalperspective view of the superconducting coils. Each of thesuperconducting coils 1 to 5 is made from a material having a highsuperconducting critical magnetic field. The closer the coils are to thesample 7, the higher will be the superconducting critical magneticfield. A protein sample 7 is inserted from above so as to be placedupright at the center portion of the magnetic field, and the magneticfield is applied to the sample from lateral directions.

Each of the superconducting magnets consists of a pair of left and rightcoils which are arranged symmetrically, and each of the coils is woundabout a horizontal axis in a solenoidal fashion. Throughout thedrawings, the left coils are designated by the same reference numeralsas the right coils with the addition of a prime (′) so that, forexample, the right coil 1 and the left coil 1′ from part of the pair ofleft coils 1′–5′ and the right coils 1–5. A solenoid coil 6 which ismade from copper and is maintained at an ordinary temperature, or asolenoid coil 6 which is Y-based or made from MgB₂ and cooled to 10 to20 K, is used for NMR signal detection. The superconducting magnets areset to a permanent current mode by a permanent current switch 10, andthe time fluctuation of the magnetic field is adjusted to be 0.5 Hz perhour or less.

The superconducting magnets are immersed in liquid helium 9 andmaintained at a low temperature. A gap between the container containingthe liquid helium 9 and the outer housing is filled with liquid nitrogen8, so that the dual structure formed of the liquid helium 9 and theliquid nitrogen 8 contributes to conserving helium.

Each of the left and right superconducting coils of the presentembodiment has a horizontal central axis and is in substantiallyconcentric relation with respect to the horizontal central axis andgenerates a horizontal magnetic field. The superconducting coils arearranged to be multilayered, and the left and right superconductingcoils in each of the layers are substantially mirror-symmetrical witheach other with respect to a center face extending along the verticaldirection of the magnet device. The direction of a current flowingthrough the superconducting coils 5 and 5′, which form the innermostlayer, together with the superconducting coils 4 and 4′, is reverse tothat of the currents of the other superconducting coils. Morespecifically, the direction of the magnetic field generated in thesample area by the superconducting coils 5 and 5′ is opposite to themain direction of the magnetic field generated by the othersuperconducting coils. Owing to this structure, the split type magnetdevice, as shown, generates a remarkably uniform magnetic field whoseuniformity is the same as or superior to that generated by conventionalmultilayer solenoids.

The foregoing description is a summary of the NMR system using a magnethaving a split coil structure according to the present invention. Onlythe structure of a superconducting coil of the NMR system is describedin each of the following embodiments.

An arrangement of superconducting coils, according to a secondembodiment of the present invention, is shown in FIG. 2. Each of thepairs of (left and right) superconducting coils 11 to 16 and 11′ to 16′(ex., the pair of 11 and 11′) is arranged so as to be substantiallyconcentric with respect to a central axis extending along the horizontaldirection. The left and right multilayer superconducting coils arearranged substantially symmetrically with respect to a center faceextending along the vertical direction of the magnet device, and acertain distance is maintained between the centerline and each of themultilayer superconducting coils. The superconducting coils 14, 15, and16 form the innermost layer, wherein the superconducting coils 15 and15′ are energized in such a manner that the magnetic field generatedthereby is in a direction reverse to that generated at the central part.Thus, a magnetic field of ppb-order uniformity is formed at the centerportion of the split type magnet device of the present embodiment.

An arrangement of superconducting coils, according to a third embodimentof the present invention, is shown in FIG. 3. Each of the pairs of (leftand right) superconducting coils 17 to 24 and 17′ to 24′ (ex., the pairof 17 and 17′) is arranged substantially concentric with respect to acentral axis extending along the horizontal direction. The left andright multilayer superconducting coils are arranged substantiallysymmetrically with respect to a center face extending along the verticaldirection of the magnet device, and a certain distance is maintainedbetween the center face and each of the multilayer superconductingcoils. Among the layers formed by the pairs of (left and right)superconducting coils, the innermost layers are formed of thesuperconducting coils 23, 23′, 24 and 24′, and layers disposed radiallyoutward from the innermost layers are formed of the superconductingcoils 20, 20′, 21, 21′, 22 and 22′. The pair of superconducting coils 22and 22′ and the pair of superconducting coils 23 and 23′ are energizedin such a manner as to generate a magnetic field which is in a directionreverse to that generated at the central part. Thus, a magnetic field ofa ppb-order uniformity is formed at the center portion of the split typemagnet device of the present embodiment.

The NMR apparatus should desirably have a small leakage magnetic field;and, therefore, a fourth embodiment, which will described hereinafter,includes a shielding of the leakage magnetic field.

An arrangement of superconducting coils according to the fourthembodiment of the present invention is shown in FIG. 4. Superconductingcoils 26 to 30 and 26′ to 30′ generate a uniform magnetic field at thecenter portion of the magnet device. In the present embodiment, thesuperconducting coil 30 and 30′ are energized to generate a magneticfield which is in a direction reverse to that generated by the othercoils, so that a magnetic field of ppb-order uniformity is generated.Superconducting shielding coils 25 and 25′ are active shielding coilsused for suppressing the leakage of the magnetic field.

An arrangement of superconducting coils and a ferromagnetic member forshielding the leakage magnetic field, according to a fifth embodiment ofthe present invention, are shown in FIG. 5. A cylindrical ferromagneticmember 31 and a disk-like ferromagnetic member 32 form magnetic paths toinhibit a magnetic field, which is generated by the superconductingcoils 18–24, 18′–24′, from leaking to the outside.

An arrangement of superconducting coils 12–16, 12′–16′ and aferromagnetic member for shielding the leakage magnetic field, accordingto a sixth embodiment of the present invention, are shown in FIG. 6.

Superconducting shield coils 34–35 and 34′–35′ inhibit the magneticfield from leaking radially outward, while the disk-like ferromagneticmember 33 inhibits the magnetic field from leaking along the axialdirection.

An arrangement of superconducting coils and a ferromagnetic member forshielding the leakage magnetic field, according to a seventh embodimentof the present invention, are shown in FIG. 7. Superconducting shieldcoils 37 and 38 and 37′ and 38′ inhibit the magnetic field from leakingalong the axial direction, while a cylindrical ferromagnetic member 36inhibits the magnetic field from leaking radially.

Although all of the coils 18–24 and 18′–24′ constituting the magnetdevice are superconducting coils throughout the foregoing embodiments,the present invention is not limited to the foregoing embodiments, andthe coils may be those which can carry a current, such as a coilfabricated by winding a copper wire. Further, a permanent magnet may beused as a source of the magnetomotive force for the static magneticfield source.

Various embodiments of the present invention are possible, as describedabove; however, the invention is not limited to the embodimentsdescribed in this specification.

According to the present invention, the NMR apparatus for solutionanalysis using a split type magnet device can generate a magnetic fieldof ppb-order uniformity in a detection space. Since it is possible toinsert a solenoid type probe coil into the magnetic field using a splitgap of the magnet device, even an apparatus of 800 MHz can achieve a SNdetection sensitivity equivalent to that of a conventional 1 GHz NMRapparatus. Further, since the intensity at the center portion of themagnetic field is relatively low, it is possible to shield the leakagemagnetic field, thereby remarkably improving the installability of theapparatus.

1. A superconducting magnet device configured for an NMR spectrometer,which comprises: a split type superconducting magnet comprising leftsolenoid superconducting magnets and right solenoid superconductingmagnets, the split type superconducting magnet having a center spacearound a vertical center axis between the left solenoid superconductingmagnets and the right solenoid superconducting magnets; a sample tubeplaced in the center space in order to enable placement of the sampletherein which is energized by a magnetic field generated by the splittype superconducting magnet; and a solenoid coil configured fordetecting signals due to magnetic resonance from the energized sample;and a permanent current switch configured for holding the split typesuperconducting magnet in a permanent current mode; wherein the leftsolenoid superconducting magnets and the right solenoid superconductingmagnets are arranged mirror-symmetrically with respect to a center facealong the vertical center axis; wherein the left solenoidsuperconducting magnets and the right solenoid superconducting magnetsare constituted respectively by a separate plurality of outermostmagnets and a separate plurality of innermost magnets; wherein theplurality of innermost magnets are sandwiched between the plurality ofoutermost magnets; wherein the plurality of innermost magnets areconstituted by a plurality of split type solenoid coils and are arrangedmirror-symmetrically with respect to a center face thereof; wherein theleft solenoid superconducting magnets and the right solenoidsuperconducting magnets are arranged symmetrically with respect to thehorizontal center axis intersecting the vertical center axis; whereinthe left solenoid superconducting magnets and the right solenoidsuperconducting magnets are arranged in concentric relation with respectto the horizontal center axis; wherein a direction of current in atleast one of the plurality of innermost magnets is minus when adirection of main current in at least one of the plurality of outermostmagnets configured for energizing the sample is plus.
 2. Thesuperconducting magnet device according to claim 1, wherein a diameterof the sample tube is in a range of 5 to 10 mm.
 3. The superconductingmagnet device according to claim 1, wherein the sample is a liquidsample.
 4. The superconducting magnet device according to claim 1,wherein the center space extends vertically and the sample tube isinserted into the center space in a vertical direction.
 5. An NMRspectrometer comprising the split type superconducting magnet accordingto claim 1, which further comprises a helium tank where the magnet isimmersed in liquid helium.
 6. The NMR spectrometer according to claim 5,which further comprises a nitrogen tank surrounding the helium tank. 7.The NMR spectrometer comprising the split type superconducting magnetaccording to claim 5, which further comprises a helium tank where themagnet is immersed in liquid helium.
 8. The NMR spectrometer accordingto claim 7, which further comprises a nitrogen tank surrounding thehelium tank.
 9. The NMR Spectrometer comprising the split typesuperconducting magnet according to claim 5, wherein the permanentcurrent switch is connected to the superconducting magnet which isimmersed in the liquid helium.
 10. The NMR spectrometer according toclaim 9, which further comprises a nitrogen tank surround the heliumtank.
 11. A superconducting magnet device configured for an NMRspectrometer, which comprises: a split type superconducting magnetcomprising left solenoid superconducting magnets and right solenoidsuperconducting magnets, the split type superconducting magnet having acenter space around a vertical center axis between the left solenoidsuperconducting magnets and the right solenoid superconducting magnets,the center space enabling placement of a sample therein which isenergized by the magnet; a sample tube having a diameter in a range of 5to 10 mm and placed in the center space configured for placing a samplewhich is energized; and a solenoid coil configured for detecting signalsdue to magnetic resonance from the energized sample, the solenoid coilbeing wound around the sample tube; and a permanent current switchconfigured for holding the split type superconducting magnet in apermanent current mode; wherein the left solenoid superconductingmagnets and the right solenoid superconducting magnets are arrangedmirror-symmetrically with respect to the vertical center axis; whereinthe left solenoid superconducting magnets and the right solenoidsuperconducting magnets are constituted respectively by a plurality ofoutermost magnets and a plurality of innermost magnets; wherein theplurality of innermost magnets are sandwiched between the plurality ofoutermost magnets; wherein the plurality of innermost magnets areconstituted by a plurality of split type solenoid coils and are arrangedmirror-symmetrically with respect to the vertical center axis; whereinthe left solenoid superconducting magnets and the right solenoidsuperconducting magnets are arranged symmetrically with respect to ahorizontal axis perpendicularly intersecting the vertical center axis;wherein the left solenoid superconducting magnets and the right solenoidsuperconducting magnets are arranged in concentric relation with respectto the horizontal axis; and wherein a direction of current flowingthrough the innermost coil is reverse to that of current flowing throughother superconducting coils.
 12. The superconducting magnet deviceaccording to claim 11, wherein the sample is a liquid sample.
 13. Thesuperconducting magnet device according to claim 11, wherein the centerspace extends vertically and the sample tube is inserted into the centerspace in a vertical direction.
 14. The superconducting magnet deviceaccording to claim 1, wherein an intensity of the magnetic field in thecenter space where the sample is placed is at least 14 T.
 15. Thesuperconducting magnet device according to claim 1, wherein an intensityof the magnetic field in the center space where the sample is placed isat least 21 T.